Polymer networks

ABSTRACT

The present invention provides catalytic polymer networks containing an active atom of tin, silicon or germanium having a high activity with reduced toxicity due to reduced leaching of the active atom from the polymer.

FIELD OF THE INVENTION

The present invention is concerned with the polymer networks andprocesses for their production. More specifically, the present inventionis concerned with polymer networks containing tin, silicon or germanium.

BACKGROUND OF INVENTION

Soluble forms of trialkyltin hydrides have been employed as reagents inthe synthesis of fine chemicals for decades despite their associated(non-regenerable) and toxic problems. It is because the Sn—H bond ishomolytically very labile such that many radical assisted organicsyntheses based on these reagents have been developed. The toxicity oftrialkyltin compounds is strongly dependent on the nature and length ofthe alkyl chains (inversely dependent on alkyl chain length). Theirtoxcity has been widely debated and has hindered the introduction of tinhydride chemistry to the synthesis of pharmaceutical products for humanconsumption. Many potential replacements have been investigated over thepast two decades but only few alternatives such as (Me₃Si)₃SiH andBu₃GeH, which display similar chemical properties to the trialkyltinhydrides, have met with any degree of success. Nevertheless, thesuperiority, versatility and selectivity at lower available costssustain trialkyltin hydrides as important industrial reagents. It isnoted the recent re-introduction of tributyltin hydride chemistry fordrug synthesis denotes the importance & unique synthetic roles of thesereagents.

For practicality, other attempts have been focussed to immobilisetrialkyltin hydride analogues, and hence combine the favourablereactivity associated with the tin and the separation capabilities ofsolid tethered reagents/catalysts. Most attention in this area hasfocused on insoluble cross-linked polystyrene supports. These haveproven to be more successful than most inorganic supports, althoughactive tin hydride loadings struggle to reach values above about 1.4mmol g⁻¹ and leaching problems cannot be completely eliminated. Few tinhydrides immobilised onto non-styrenic polymer supports have beenreported. The key point to note concerning all previous support methods,is that the tin centre is only bound by a single covalent Sn—C bond tothe polymer. Cleavage of this linkage, by any given mechanism such asbeta-elimination, will inevitably allow product contamination with thesoluble tin compounds.

SUMMARY OF THE INVENTION

In a first aspect of the present invention there is provided a polymercomprising a structural unit (1)

wherein R is individually selected from divalent hydrocarbon radicals;R¹ is selected from the group consisting of monovalent hydrocarbonradicals, organic polymers and inorganic polymers;R² is individually selected from divalent hydrocarbon radicals;M is a tin, silicon or germanium atom, preferably tin or silicon, morepreferably tin;X is selected from H, Cl, Br and I;Y is selected from H, Cl, Br and I;m is an integer of 1 or 2;p is an integer of 1 or 2;q is an integer of 1 or 2;r is an integer of 0 or 1; and,wherein m+p+q+r=4.

In a second aspect of the present invention there is provided a polymercomprising a structural unit (2)

wherein R is individually selected from divalent hydrocarbon radicals;R¹ is selected from the group consisting of monovalent hydrocarbonradicals, H, Cl, Br, I, organic polymers and inorganic polymers;M is a tin, silicon or germanium atom, preferably tin or silicon, morepreferably tin; and,m is an integer of 1-4.

In a further aspect of the present invention, there is provided aprocess for the production of a polymer comprising a structural unit(2), comprising reacting a diGrignard reagent having the formula (3)XM′(R)M′X  (3)wherein X is individually selected from the group consisting of Cl, Brand I;M′ is individually selected from the group consisting of Group IImetals, Group XI metals, Group XII metals and mixtures thereof; and,R is selected from divalent hydrocarbon radicals;with a compound having the formula (4)R¹ _(a)MX′_(b)  (4)wherein R¹ is selected from the group consisting of monovalenthydrocarbon radicals, H, organic polymers and inorganic polymers;M is a tin, silicon or germanium atom, preferably tin or silicon, morepreferably tin;X is individually selected from the group consisting of Cl, Br and I;X′ is individually selected from the group consisting of Cl, Br and I;a is an integer of 0-2; and,b is an integer of 2-4.

In a further aspect of the present invention, there is provided aprocess of production of a polymer comprising a structural unit (1),wherein X and Y are selected from Cl, Br and I, comprising reacting acompound having formula (2) with a compound selected from a chlorinatingagent, a brominating agent and an iodinating agent.

In a further aspect of the present invention, there is provided aprocess of production of a polymer comprising a structural unit (1),wherein X and Y are H, comprising reacting a polymer comprising astructural unit (1), wherein X and Y are selected from Cl, Br and I,with a reducing agent that is a hydride source.

The polymers of the present invention preferably comprise polymernetworks. The polymers and polymeric networks according to the presentinvention are organometallic composites. The inorganic component is tin,silicon or germanium, and the organic being the divalent and monovalenthydrocarbon moieties interconnecting the inorganic component.

According to a further aspect of the present invention, there isprovided a polymer comprising the structural unit (5)(HSi)_(n) (5)wherein n is an integer.

In compounds having a unit (5), preferably n is an integer of 3-1000000,more preferably 10-100000, more preferably 50-50000, more preferably200-10000.

According to a further aspect of the present invention, there isprovided a process for the production of a polymer comprising astructural unit (5)(HSi)_(n)  (5)wherein n is an integer;comprising reducing a compound having the formula (6)HSiX″₃  (6)wherein X″ is individually selected from the group consisting of Cl, Brand I, preferably Cl.

The reducing agent used to produce compound (5) is preferably an ionicmetal containing compound. Particularly preferred compounds includeionic metal-hydrocarbon pairs, preferably selected from the groupconsisting of ionic Group I, II, XI and XIII metal-hydrocarboncompounds. Preferably, the metal forms the cationic moiety and thehydrocarbon forms the anionic moiety.

Preferred metals used in the ionic Group I, II, XI and XIIImetal-hydrocarbon compounds include Li, Na, K, Mg, Ca, Cu, Hg and Zn.

Preferred anionic hydrocarbons include cyclohexenyl, benzyl, phenylethyland phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl,ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl,phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl,aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl anions. Aparticularly preferred reducing agent is sodium naphthalenide.

The present invention provides or may be used to construct catalystsystems. The fundamental principle is based on building a catalyst thatcontains the active site as part of the polymer or polymeric networkbackbone. As used herein, the term “catalyst” refers to a compound thatspeeds a chemical reaction or causes it to occur. The catalysts of thepresent invention are formally organometallic compounds. Certain typesof the organometallic compounds of the invention will require“activation” prior to being catalytically active. Other organometalliccompounds of the invention will be “activator-free catalysts” and willnot require activation prior to being catalytically active.

The catalytic polymers of the present invention are preferablyhydrogenation catalysts. For example, they may be used to hydrogenateunsaturated systems such as aldehydes, ketones and olefins.Alternatively, they may be used in the hydrogenation of halogenatedhydrocarbons via a halogen displacement reaction.

A polymer according to the present invention preferably comprises one orboth of the following structures

wherein R, R¹, R², M, X, Y, m, p, q and r are as defined above, andwherein n is an integer. Preferably, n is an integer of 10-100000, morepreferably 50-50000, more preferably 200-10000. Preferably, n is of amagnitude capable of rendering the polymer substantially insoluble inorganic solvents.

The polymers of the present invention are preferably substantiallyinsoluble in organic solvents. Thus, the production of heterogenouscatalysts is facilitated.

In the above structures and formulas (1)-(6):

R is preferably selected from the group consisting of C₁₋₂₀ alkanediyl,C₂₋₂₀ alkenediyl, C₂₋₂₀ alkynediyl, C₃₋₃₀ cycloalkanediyl, C₃₋₃₀cycloalkenediyl, C₅₋₃₀ cycloalkynediyl, C₇₋₃₀ alkarylenediyl and C₅₋₃₀arylenediyl, any of which may be optionally substituted with one or moreheteroatoms in the carbon backbone.

R is more preferably selected from the group consisting of C₁₋₁₅alkanediyl, C₂₋₁₅ alkenediyl, C₂₋₁₅ alkynediyl, C₄₋₂₀ cycloalkanediyl,C₄₋₂₀ cycloalkenediyl, C₅₋₂₀ cycloalkynediyl, C₇₋₂₀ alkarylenediyl andC₆₋₂₀ arylenediyl, any of which may be optionally substituted with oneor more heteroatoms in the carbon backbone.

R is more preferably selected from the group consisting of straightchain C₁₋₁₅ alkanediyl, C₂₋₁₅ alkenediyl and C₆₋₁₅ alkarylenediyl.

Most preferably, R is selected from 1,6-hexylene, 1,8-octylene,1,10-decylene and 1,12-dodecylene.

Preferably substantially all groups R are the same.

The term “alkanediyl” refers to a straight or branched saturateddivalent hydrocarbon radical having the number of carbon atomsindicated.

The terms “alkenediyl” and “alkynediyl” refer to straight or branched,unsaturated divalent hydrocarbon radicals. An “alkenediyl” ischaracterized by a carbon-carbon double bond and an “alkynediyl” ischaracterized by a carbon-carbon triple bond.

The term “cycloalkanediyl” refers to a cyclic saturated divalenthydrocarbon radical having the number of carbon atoms indicated.

The terms “cycloalkenediyl” and “cycloalkynediyl” refer to cyclicunsaturated divalent hydrocarbon radicals. A “cycloalkenediyl” ischaracterized by a carbon-carbon double bond and a “cycloalkynediyl” ischaracterized by a carbon-carbon triple bond.

The term “arylenediyl” refers to a divalent unsaturated aromaticcarbocyclic radical having one or two rings.

The term “alkarylenediyl” refers to a divalent unsaturated mono- ordi-alkyl-substituted aromatic carbocyclic radical having one or tworings.

R¹ is preferably selected from the group consisting of C₁₋₂₀ alkyl,C₁₋₂₀ alkoxy, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₃₋₃₀ cycloalkyl, C₃₋₃₀cycloalkenyl, C₄₋₃₀ cycloalkynyl, C₇₋₃₀ alkaryl, C₅₋₃₀ aryl, C₅₋₃₀aryloxy, any of which may be optionally substituted with one or moreheteroatoms in the carbon backbone, organic and inorganic polymers.

R¹ is more preferably selected from the group consisting of C₁₋₁₅ alkyl,C₁₋₁₅ alkoxy, C₂₋₁₅ alkenyl, C₂₋₁₅ alkynyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀cycloalkenyl, C₄₋₂₀ cycloalkynyl, C₇₋₂₀ alkaryl, C₆₋₂₀ aryl, C₆₋₂₀aryloxy, any of which may be optionally substituted with one or moreheteroatoms in the carbon backbone, organic and inorganic polymers.

R¹ is more preferably selected from the group consisting of straightchain C₁₋₁₀ alkyl, C₁₋₁₀ alkoxy, C₂₋₁₀ alkenyl, C₆₋₁₂ aryl, C₆₋₁₂aryloxy and organic polymers.

Most preferably, R¹ is selected from the group consisting of methyl,ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl,norbornyl and adamantyl, vinyl, propenyl and cyclohexenyl, benzyl,phenylethyl and phenylpropyl, phenyl, tolyl, dimethylphenyl,trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl,methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl,acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl,biphenylyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, phenoxy,1,2-dimethylbutoxy, most preferably phenyl and phenoxy.

Each R¹ may be the same or different, preferably the same.

The term “alkyl” refers to a straight or branched saturated monovalenthydrocarbon radical having the number of carbon atoms as indicated.

The term “alkoxy” refers to the group “alkyl-O-”, where alkyl is asdefined above.

The term “alkenyl” refers to a straight or branched unsaturatedmonovalent hydrocarbon radical having the number of carbon atoms asindicated and the distinguishing feature of a carbon-carbon double bond.

The term “alkynyl” refers to a straight or branched unsaturatedmonovalent hydrocarbon radical having the number of carbon atoms asindicated and the distinguishing feature of a carbon-carbon triple bond.

The term “cycloalkyl” refers to a cyclic saturated monovalenthydrocarbon radical having the number of carbon atoms as indicated.

The terms “cycloalkenyl” and “cycloalkynyl” refer to cyclic unsaturatedmonovalent hydrocarbon radicals. A “cycloalkenyl” is characterized by acarbon-carbon double bond and a “cycloalkynyl” is characterized by acarbon-carbon triple bond.

The term “aryl” refers to a monovalent unsaturated aromatic carbocyclicradical having one or two rings, such as phenyl, naphthyl, indanyl orbiphenyl, or to a monovalent unsaturated aromatic heterocyclic radicalsuch as quinolyl, dihydroisoxazolyl, furanyl, imidazolyl, pyridyl,phthalimido, thienyl and the like.

The term “aryloxy” refers to the group “aryl-O—”, where aryl is asdefined above.

A non-limiting list of organic and inorganic polymers that R¹ maycomprise includes polyacetals, polyamides, polyimides, polyesters,polycarbonates, polyamide-imides, polyamide-esters, polyamide ethers,polycarbonate-esters, polyamide-ethers, polyacrylates; elastomers suchas polybutadiene, copolymers of butadiene with one or more othermonomers, butadiene-acrylonitrile rubber, styrene-butadiene rubber,polyisoprene, copolymers of isoprene with one or more other monomers,polyphosphazenes, natural rubber, blends of natural and syntheticrubber, polydimethylsiloxane, copolymers containing the diphenylsiloxaneunit; polyalkylmethacrylates, polyethylene, polypropylene, polystyrene,polyvinylacetate; polyvinylalcohol, polyvinylchloride, silica andalumina. Such polymers preferably comprise part of a support for thepolymer of the present invention.

R² is preferably individually selected from the same groups as R, andmay be substantially the same or different.

X is preferably individually selected from the group consisting of Br, Iand H, most preferably Br and H.

Y is preferably individually selected from the group consisting of Br, Iand H, most preferably Br and H.

X′ is preferably Cl.

For structure (1), m is preferably 2. For structure (2), m is preferably3 or 4, more preferably 3.

p is preferably 1.

q is preferably 1.

Where p and q are 1, r is preferably 0.

M′ is preferably selected from magnesium, calcium, mercury and copper,most preferably magnesium.

a is preferably 0 or 1.

b is preferably 3 or 4.

Preferred chlorinating, brominating and iodinating agents are therespective molecular halogens, i.e., Cl₂, Br₂, I₂.

Preferred reducing agents used in the process for the production of apolymer comprising a unit (1) include the borohydrides, aluminiumhydrides and boranes. Exemplary reducing agents include Lithiumaluminium hydride, sodium borohydride, sodium hydride, boranes,selectride, lithium borohydride, sodium cyanoborohydride, sodiumnaphthelenide, DIBAL-H and REDAL-H.

The reduction reaction of the substrate species is preferablyfacilitated with a radical intitiator. Exemplary initiators include2,2′-azobisisobutyronitrile (AIBN), benzoyl peroxide, tert-butylperacetate, peracetic acid, tert-amyl peroxybenzoate,tert-butylperoxide, cyclohexanone peroxide and the like.

Compounds having a structural unit (1), more preferably comprise astructural unit (7) and/or (8)

wherein R is individually selected from the group consisting of H,methyland propyl, preferably H;X is Cl, Br or I; and,n is an integer of 1-20, preferably 1-12, more preferably 6, 8, 10, or12.

Compounds having a structural unit (2), more preferably comprise astructural unit (9) and/or (10)

wherein R is individually selected from the group consisting of H,methyl and propyl, preferably H;R¹ is selected from the group consisting of C₆₋₁₀ aryl and C₆₋₁₀aryloxy, preferably phenyl and phenyloxy; and,n is an integer of 1-20, preferably 1-12, more preferably 6, 8, 10, or12.

Molecular weights of the polymers according to the present invention arepreferably in the range of 100-10000000, more preferably in the range of1000-1000000, more preferably in the range 10000-100000.

In a particularly preferred embodiment of the present invention,polymeric networks containing tin hydrides are produced. Such networksare preferably prepared in a multi-step process.

In a preferred process, a diGrignard reagent is prepared via a knownmethod from a species such as an n-dihaloalkane, wherein n is the numberof carbon atoms in the alkane. For example 1,12-dibromododecane and1,6-dibromodohexane are preferred reagents. The diGrignard reagent ispreferably prepared using magnesium metal in aprotic solvents, forexample etheric solvents such as diethyl ether, THF and the like.

In a first stage, the diGrignard is preferably reacted with a tin,silicon or germanium halide, for example a tin chloride based speciessuch as SnCl₄, PhSnCl₃ or PhOSnCl₃. This forms a polymeric network thatcan then be treated in a second step with a halogenating agent, forexample, a molecular halogen such as bromine or iodine, to remove thephenyl groups and/or to introduce tin, silicon or germanium halidefunctionalities, e.g. tin bromide functionalities into the network. In athird step, or a step concurrent with the second step, the tin, siliconor germanium halide groups may then be reduced with a hydride donorreducing agent, for example, sodium borohydride, to form thecorresponding tin, silicon or germanium hydride groups.

Preferred solvents for the multi-step process include ethers, forexample diethyl ether, tetrahydrofuran and diphenyl ether. Preferablythe multi-step process is carried out under substantially dry conditionswith dry solvents. Further, the above mentioned processes may be carriedout under an inert atmosphere, for example, nitrogen or argon.

The polymeric network produced may be used for catalysis. Both thepolymers and the polymeric networks are preferably insoluble, and arepreferably capable of swelling in organic solvents. As the solvents usedfor swelling, there may be mentioned, for example, hydrocarbon solventssuch as benzene and toluene; ether type solvents such as diethyl ether,tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene;halogenated hydrocarbon solvents such as methylene chloride, chloroformand chlorobenzene; ketone type solvents such as acetone, methyl ethylketone and methyl isobutyl ketone; alcohol type solvents such asmethanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butylalcohol; nitrile type solvents such as acetonitrile, propionitrile andbenzonitrile; ester type solvents such as ethyl acetate and butylacetate; carbonate type solvents such as ethylene carbonate andpropylene carbonate; and the like. These may be used singly or two ormore of them may be used in admixture.

Due to the highly cross-linked nature of the networks, they areconsidered to have greater mechanical robustness over known insolublepolymers. Further, due to the flexibility of the material, they are moredurable than highly rigid inorganic supports such as high surface areasilicas that may be crushed.

Some of the advantages attributable to various of the polymer networksaccording to the present invention include facilitated separation of thepolymers from the polymer production mixture, the reduction of leachingof tin from the reagent and catalyst materials, reduced toxicity of thepolymers, superior mechanical, thermal and chemical stability overequivalent prior art catalysts, and a high selectively of reactions.

BRIEF DESCRIPTION OF THE FIGURES

By way of example only, the benefits of the invention will now beillustrated by reference to the accompanying drawings in which:

FIG. 1 graphically represents the catalytic activity of polymeric tinhydride for polymer tin network 12b prepared according to Example 4wherein the left hand vertical axis of the graph is a scale of thepercentage activity and the right hand vertical axis is a scale for theactivity in terms of mmolg⁻¹;

FIG. 2 graphically represents the selectivity of polymeric tin hydridefor polymer tin network 12b; and

FIG. 3 graphically represents the swelling properties of polymeric tinnetwork 11 prepared according to Example 1.

DETAILED DESCRIPTION OF THE INVENTION

The invention will now be illustrated by the following Examples whichare not intended to limit the scope of protection obtained.

EXAMPLES

The basic experimental procedure is similar to that employed for thesynthesis of a fluorous tin hydride used by Dennis P. Curran [Dennis P.Curran, Masahide Hoshino, Journal of Organic Chemistry, 1996, Vol 61,p6480-6481]. A diGrignard is prepared and allowed react with a tin basedspecies preferably containing three or more tin chloride bonds. At theend of the reaction unreacted tin chloride bonds may be converted to tinhydroxyls and the unreacted Grignard functionalities may be converted tocarbon-hydrogen groups by the addition of either saturated ammoniumchloride or 2.0 molar hydrochloric acid. The samples are preferablyfiltered and washed with de-ionised water to remove any acid and thenwith diethyl ether to remove any soluble polymers and very small(soluble) fragments of the polymeric network. The diethyl ether isallowed to evaporate from the samples in air before they are placed inthe oven at 100° C. until dry (about 2 h), the samples are then treatedagain with 2.0 molar hydrochloric acid and a small amount of diethylether. The diethyl ether is used to swell the network and release anymagnesium or magnesium dihalide particles. It is also believed that thisprocess helps to purify the samples by the removal of any tin oxidecharacter although this has not been confirmed. Tin oxide characterarises due to the presence of tin hydroxyl groups that can undergocondensation giving tin-oxygen-tin bridging units.

For all methods, all solvents are distilled, dried and degassed. Allglassware, stirrer bars, and anti-bumping granules are dried in an ovenand the apparatus is set up whilst still hot, under a purge of nitrogen.The formation of the diGrignards was always initiated with applicationof a combination of anti-bumping granules and iodine vapour treatment tothe magnesium. At the end of the reaction all materials were treatedwith a similar work-up procedure; The solids were filtered and washedwith de-ionised water or methanol and diethyl ether before the diethylether was allowed to evaporate in air at room temperature from thesolid, the materials were then dried at 100° C., cooled and treated with2.0 molar hydrochloric acid and diethyl ether, then washed withde-ionised water and dried at 100° C. under vacuum.

Reagents

Phenyltin trichloride was prepared as follows; bromobenzene (Aldrich) indiethyl ether (Fisher) was added to iodine (BDH) pre-treated magnesiumturnings (Aldrich). The reaction was initiated with gentle warming andturned deep red in colour shortly after the appearance of the magnesiumsalt. The Grignard reagent was stirred at room temperature for 1 hbefore the solution was cooled in a dry ice/acetone (BDH) bath and tin(IV) chloride (Lancaster) in diethyl ether added. This was heated underreflux overnight and at room temperature, saturated ammonium chloride(BDH) added. The white solid was collected by filtration, and theorganic layer was washed with water before the solvent was removed. Allsolids were combined and recrystallised from chloroform (Fisher) toyield the pure Ph4Sn. Tetraphenyltin was reacted with tin (IV) chloridein a 1:3 molar ratio at 150° C. for 3 h, the phenyltin trichloride wasthen vacuum distilled to yield the pure product as in accordance withthe literature. [Henry Gilman and Lewis A. Gist, Jr, Journal of OrganicChemistry, 1957, 22, 368] Proton NMR spectroscopy revealed the productto be 96% pure, with the only observable impurities being partiallyhydrolysed product although this is most likely to have occurred duringthe preparation of the sample for NMR spectroscopy. (spectrum recordedin CDCl₃ (Cambridge Isotope Laboratories)) The diGrignard reagents werealways prepared from their corresponding dihalide, 1,12-dibromododecane(Acros), 1,10-diiododecane (Acros), 1,8-dibromooctane (Acros),1,6-dibromohexane (Lancaster). 2.0 molar hydrochloric acid was dilutedfrom concentrated hydrochloric acid (Fisher). Other reagents, bromine(Aldrich), sodium borohydride (Aldrich), ethanol (BDH), methanol(Fisher), 1-butanol (Acros), 1-iodooctane (Lancaster), octane (Aldrich),cyclohexane (Fisher).

Example 1

Method A; Synthesis of Sn((CH₂)_(n))_(4/2) (11) Type Polymeric Networks

Typically about 10% of X(CH₂)_(n)X, where X═Br or I and n=6,8,10 or 12in diethyl ether was added to the magnesium that had been pre-treatedwith iodine vapour. The reactions were stirred at room temperature,after about 1 minute of stirring the reactions self initiated and theremaining dihalide was slowly added at room temperature with vigorousstirring. After the final addition of the dihalides, the diGrignardswere stirred for 1 h to ensure the complete formation of the reagent.The diGrignards were then cooled in a dry ice/acetone bath before tin(IV) chloride was added directly to the stirred solution, this wasallowed to warm to room temperature and then heated under reflux for 10minutes. The solution containing the polymeric networks was then cooledto room temperature and saturated ammonium chloride added. Typically,0.350 g, 14.6 mmol Mg, 1.70 g, 6.97 mmol Br(CH₂)₆Br, and 0.41 ml, 0.91g, 3.5 mmol SnCl₄ were used for the synthesis of Sn((CH₂)₆)_(4/2).

Preparation of Sn((CH₂)₆)_(4/2) (11) Polymeric Networks

The following polymeric networks (Sn((CH₂)₆)_(4/2)) (11) shown in Table1 were prepared by ‘method A’ to establish the best synthesis conditionsfor activity and resistance to bromine degradation. TABLE 1 PolymericAssumed diGrignard Mg SnCl₄ in network yield in % Br(CH₂)₆Br in g in gml A1 120 1.42 0.29 0.41 (excess of Sn—Cl bonds) A2 110 1.55 0.32 0.41A3 100 1.70 0.35 0.41 A4  90 1.89 0.39 0.41 A5  80 2.13 0.44 0.41(excess of RMgX groups)

To samples of each network, 60 μl bromine was added in diethyl ether (10ml) and stirred until the solution was clear. The solid were washedtwice with diethyl ether (2×10 ml) and the soluble fraction collected.The polymer was treated with sodium borohydride (0.200 g, 5.26 mmol) inethanol (20 ml) and heated under reflux overnight. This was then washedwith methanol (4×10 ml) and 1-butanol (2×5 ml) to be certain of removingany traces of the sodium borohydride. 1-Butanol (10 ml), 1-iodooctane(200 μl, 1.38 mmol) and 2,2-azobisisobutyronitrile (AIBN) were added andthe reaction heated to 80° C. overnight. The polymeric networks werefiltered and the liquid collected for gas chromatography analysis.Samples were also sent for ICP analysis to determine the degree of tincontamination.

Table 2

Resistance of (11) to degradation by bromine. Polymeric network Massused, mmol of tin % loss* A1 0.4050 g, 1.41 mmol 89 A2 0.4059 g, 1.41mmol 75 A3 0.3215 g, 1.12 mmol 39 A4 0.3373 g, 1.18 mmol 49 A5 0.3684 g,1.28 mmol 47*percent loss relative to 1 molar equivalent of Br₂.

In general, it can be observed from Table 2 that a greater incorporationof the organic phase results in a material that possesses an enhancedresistance to chemical breakdown as a result of bromination. TABLE 3Activity of the polymeric tin hydride (11). Polymeric network Active tinas SnH in % Active SnH in mmol g⁻¹ A1 No data No data A2 No data No dataA3 41.3 1.43 A4 50.2 1.74 A5 32.9 1.14

The results in Table 3 show that the material prepared assuming a 90%yield of diGrignard (ie 1/0.9=1.11 times excess) was found to have thebest active tin hydride content.

Example 2

Method B; Synthesis of PhSn((CH₂)_(n))_(3/2) (11′) type polymericnetworks.

Typically about 10% of X(CH₂)_(n)X, where X═Br or I and n=6,8,10 or 12in diethyl ether was added to the magnesium that had been pre-treatedwith iodine vapour, and the diGrignards formed as described according tomethod A. Interestingly the diGrignards formed a biphasic mixture with apale brown layer under a clear layer in the case of the shorterhydrocarbon linkers, n=6 and 8. These diGrignards were cooled in a dryice/acetone bath and phenyltin trichloride in diethyl ether added, thiswas then heated under reflux for 30 min before saturated ammoniumchloride was added at room temperature. This gave a rubbery whitematerial contaminated with magnesium that was later removed with 2.0molar hydrochloric acid. Typically, 0.589 g, 24.2 mmol Mg, 2.890 g, 11.8mmol Br(CH₂)₆Br, 1.97 g, 6.5 mmol PhSnCl₃ for the synthesis ofPhSn((CH₂)₁₂)_(3/12).

Example 3

Method C; Alternative Synthesis of PhSn((CH₂)₁₂)_(3/2) (11′) PolymericNetwork.

The fundamental principle of this methodology is that the diGrignard isadded to the tin compound causing tin atom cross-linking earlier duringthe network formation. The major advantages of this method are that aminimum of magnesium turnings become entrapped inside the polymericnetwork, and that cross-linking occurs at the beginning of the additionrather than at the end, hence the material is of better structuralintegrity.

Decomposition of the phenyltin trichloride in the presence of magnesiummetal is also substantially avoided by this method. The diGrignard isprepared in a minimum of solvent and is added to the phenyltintrichloride that is dissolved also in a minimum of solvent, the use of aminimum of solvent gives rise to much improved yields. The eliminationof magnesium from the material is advantageous for organic synthesis asalkali metals can cause coupling of tin halides (R₃SnX) that are presentwhen the tin hydride is used catalytically.

A 1.67 times excess of diGrignard was used as to add the diGrignard in asuitable excess (the material produced from the reaction using a 1.11times excess of diGrignard became very brittle after drying, presumablydue to the presence of significant numbers of tin-oxygen-tin bridgesarising from hydroxyl groups).

1,12-dibromododecane in a minimum of diethyl ether was added tomagnesium that had been pre-treated with iodine vapour in a shlenckflask. The diGrignard was stirred at room temperature for 2 h before itwas added to phenyltin trichloride also in a minimum of diethyl ether.The white solid was heated under reflux for 2 h without stirring beforethe material was filtered and washed with de-ionised water and diethylether. The network was dried at 100° C. (this caused a hardening of thenetwork) then washed in 2.0 molar hydrochloric acid with a littlediethyl ether followed by water and diethyl ether and dried at 100° C.in a vacuum oven. Typically, 0.281 g, 11.7 mmol magnesium, 1.83 g, 5.58mmol 1,12-dibromododecane, 0.675 g, 2.23 mmol phenyltin trichloride.

Example 4

Synthesis of XSn(R)_(2/2)RH, (12) where X═Br (a) or H (b) type polymers

Polymeric networks of the form Sn(R)_(4/2) (11) (R═(CH₂)_(n), n=6, 8, 10or 12) were swollen in diethyl ether and treated with bromine. Once thesolutions were no longer coloured, the polymers were washed with diethylether and treated with sodium borohydride in ethanol at 80° C. for 6 h.The polymers were then extensively washed with methanol (usually 4times) and then with 1-butanol (usually 2 times).

Feasibility Test for Catalytic Use of the Polymeric Networks

PhSn((CH₂)₁₂)_(3/2) (11′) (0.400 g, 0.892 mmol) was swelled in diethylether (10 ml) and bromine (46 μl, 143 mg, 0.897 mmol) added. This wasstirred overnight, washed with diethyl ether (2×10 ml), and sodiumborohydride (0.200 g, 5.26 mmol) in ethanol (20 ml) added and stirredovernight. The tin hydride was washed thoroughly with diethyl ether,methanol and 1-butanol before 1-butanol (10 ml), 1-iodooctane (200 μl,1.38 mmol) and 2,2-azobisisobutyronitrile (AIBN) were added. This washeated to 80° C. for 28.5 h before the reaction was cooled, the catalystfiltered out and washed with 1-butanol. 23 ml was collected and this wasanalysed by gas chromatography to obtain the active tin hydride contentby the amount of octane produced, and by ICP (inductive coupling plasma)to determine the degree of tin leaching.

The GC results revealed that 0.574 mmol of n-octane had been produced,0.892 mmol of catalyst had been initially used, however, material islost during the bromination step due to slight decomposition of thenetwork, and some catalyst was lost during the washing stages. Theamount of catalyst recovered was therefore used for the activitycalculations. 0.618 mmol of catalyst was recovered, this gives thematerial a tin hydride activity 92.8%, and an active tin hydrideconcentration of 2.50 mmol g⁻¹. The most active heterogeneous tinhydride in the literature is quoted at 1.4 mmol g⁻¹. The solution wasfound to contain levels of tin that were below the detection limits ofthe ICP (inductive coupling plasma) instrument.

Very similar experiments were performed for the PhSn((CH₂)₁₂)_(3/2)network. Samples were prepared according to ‘method B’ as shown in Table4. TABLE 4 Assumed yield of Grignard Br(CH₂)₁₂Br PhSnCl₃ Experimentyield % in g Mg in g in g B1 120 0.915 0.1406 0.675 (excess of Sn—Clbonds) B2 110 0.998 0.1534 0.675 B3 100 1.098 0.1688 0.675 B4 90 1.2200.1875 0.675 B5 80 1.373 0.2109 0.675 (excess of RMgX groups)

To samples of each of the polymeric networks in diethyl ether (10 ml),bromine at a ratio of 0.839, bromine to tin, was added at roomtemperature and stirred until the solution was clear. During thebromination, any magnesium in the samples was removed, presumably toMgBr₂. The samples were then washed with diethyl ether (2×10 ml) andsodium borohydride (0.050 g, 1.3 mmol) in ethanol (20 ml) added. Thiswas then heated under reflux (80° C.) for 6 h before the samples werewashed with methanol (4×10 ml) and 1-butanol (2×5 ml). 1-Butanol (10ml), 1-iodooctane (150 μl, 1.03 mmol) and 2,2-azobisisobutyronitrilewere then added and the reaction heated to 80° C. for 6 h. The reactionswere then cooled in ice and the solutions filtered, the volume measuredand the results analysed by gas chromatography. Samples were also sentfor ICP (inductive coupling plasma) analysis to determine the degree oftin contamination. TABLE 5 Resistance of PhSn((CH₂)₁₂)_(3/2) (11′) todegradation by bromine. Polymer Mass, mmol Br₂ in μl % loss after Br₂ B10.1186 g, 0.265 mmol 11.4 8.67 B2 0.1991 g, 0.444 mmol 19.1 9.05 B30.2813 g, 0.628 mmol 27.0 9.88 B4 0.1119 g, 0.250 mmol 10.7 11.1 B50.2227 g, 0.497 mmol 21.4 12.2

It is clear from Table 5 that the resistance to chemical break down bybromine of this polymeric network is much superior over the networkprepared from tin tetrachloride, that is converted to lightlycross-linked polymers upon treatment with bromine. This network retainsits highly cross-linked structure by the selective cleavage of the Ph—Snbonds by bromine over the backbone tin-carbon bonds. TABLE 6 Activity ofthe polymeric tin hydride (12b). Polymer Active tin as SnH in % ActiveSnH in mmol g−1 B1 40.0 1.08 B2 45.3 1.22 B3 60.7 1.63 B4 46.6 1.25 B527.6 0.74

It can be seen from Table 6 that in the case of this polymeric network,the material that was found to be most active was that prepared byassuming a 100% yield of diGrignard. Due to the greater length of thehydrocarbon linker chain, the tin hydride loading is less than thatobserved for the polymers A3 to A5. This is summarised in FIG. 1.

Solid Tin Hydride Selectivity

Hydrogenation of 6-bromohexene to Methylcyclopentane

Approximately 1 g of previously used polymeric network in the form ofSnI (ISn((CH₂)₁₂)_(3/2)) was regenerated to the tin hydridediisobutylaluminium hydride (20 wt % in toluene, used in excess) andwashed with water and toluene. The hydride was characterised by infraredand proton NMR spectroscopy. To the dry hydride, 6-bromohexene (100 μl,123 mg, 0.747 mmol) and isododecane (Avacado) (100 μl) as an internalstandard, and 2,2-azobisisobutyronitrile (5.5 mg, ˜6 mol %) was added intoluene. The reaction was heated at 40° C. and samples takenperiodically for analysis by gas chromatography.

Selectivity, Hexene 67.1%, methylcyclopentane 32.9%, final mass balance96%.

The conversion of the 6-bromo-1-hexene was excellent, no detectablelevel remaining at the end of the reaction. The selectivity was howevernot as good as that reported for tributyltin hydride under similarconditions. The hydride concentration in the solid network is too highto allow time for the free radical rearrangement to take place beforethe hydrogen transfer step. Essentially, R_(h) (rate of hydrogentransfer to the hexenyl radical) is too fast compared with R_(r) (rateof intermolecular free radical rearrangement) due to the highconcentration of tin hydride inside the material. These reactions aresummarised in FIG. 2. TABLE 7 Recycling of the Catalyst: Catalystprepared by ‘method C’ Cycle Activity % mmol g⁻¹ 1 24.6 0.66 2 31.0 0.833 30.8 0.83 4 32.7 0.88 5 26.6 0.71

It can be seen from the data in Table 7 that the material prepared by‘method C’ clearly does not deactivate over successive recycling. Theactivity is retained at around 30% active tin hydride. TABLE 8 Leachingdata of a material prepared by ‘method C’ obtained by ICP Cycle Leachingas Mol % of total tin in catalyst 1 Nil 2 0.00156 3 Nil 4 Nil 5 Nil

It can be seen from the data in Table 8 that the degree of tin leachingfrom this material is extremely low. The only tin contamination isbelieved to arise simply from the Mill Stone effect that is welldocumented.

Swelling Properties

A swelling study on a PhSn((CH₂)₁₂)_(3/2) (11′) network was performed ona materical prepared by ‘method C’, solvent was added to the polymericnetwork until the material was saturated, the weight of the material wasrecorded before and after the addition of solvent. TABLE 9 SolventSwelling g g−1 Swelling ml g−1 Chloroform 7.71 5.17 Toluene 4.28 4.95Ether 2.39 3.39 Hexane 1.87 2.84 Methanol 1.62 2.05 Butanol 1.44 1.78Dimethylformamide 0.73 0.77

The results presented in Table 9 are for the catalyst precursor thatcontains a phenyl groups attached to the tin centres, the high swellingcaused by toluene highlights this. The general trend is that the morehydrophobic solvents cause greater swelling of the network. The materialremained white in the presence of all solvents except toluene andchloroform, in the presence of which the material become ‘gel-like’ andpartially transparent. The swelling properties of PhSn((CH₂)₁₂)_(3/2),are summarised in FIG. 3.

Variation of the Reflux Period During the Network Formation

PhSn((CH₂)₁₂)_(3/2) (11′) was prepared using a 1.67 times excess ofdiGrignard for each preparation and the diGrignard was added to the tincompound. The reflux time period was varied and the activities at a1.38:1 Bromine to tin ratio were assessed. TABLE 10 Time Tin utilisationas % mmol g−1 % loss 24 69.0 1.28 10.4 16.3 47.0 0.87 9.9 4 43.2 0.8016.7 1 36.6 0.68 9.1

The results in Table 10 clearly indicate that increasing the reflux timeperiod increases the activity.

Varying the Ratio of Inorganic to Organic Components inPhSn((CH₂)₁₂)_(3/2) (11′)

The diGrignard of 1,12-dibromododecane was prepared in diethyl ether (15ml) and stirred for 1 h, this was added to phenyltin trichloride indiethyl ether (5 ml) without stirring. The flash was shaken to mix thereagents before being heated under reflux for a period of 2 h. At theend of each reaction the material was cooled to room temperature and 2.0molar hydrochloric acid added. Once the excess magnesium had dissolvedthe materials were filtered and washed with water and diethyl ether andthen dried in a vacuum oven at 110° C. TABLE 11 Tin compositions AssumeddiGrignard Tin loading in Max Sn—H loading in yield as % mmol g-1 mmolg-1 40 1.21 1.33 50 1.43 1.60 60 1.62 1.85 70 1.80 2.09

Assuming that the tin content in the solid is the same as the content ofthe respective precursors. TABLE 12 Assumed diGrignard Sn—H loading inmmol yield as % Tin utilisation as % g-1 40 52 0.69 50 42 0.67 60 130.23 70 7.5 0.16

Table 12 shows that using greater excesses of the organic component ofthe networks was found to produce an material with a greater tinutilisation and subsequently higher loading of tin hydride.

Example 5

Preparation of a Solid Organosilane Network

Method D, SiCl₄ and BrMg(CH₂)₁₂MgBr

The below detailed experiment was carried out with the aim of preparingan insoluble solid organosilane network containing unreacted siliconchloride groups that could be later reduced to give silicon hydridefunctions.

A 1.67 times excess of the diGrignard of 1,12-dibromododecane (3.00 g,9.15 mmol and magnesium, 0.48 g, 2.0 mmol) was prepared in diethyl etherand added to silicon tetrachloride in diethyl ether at room temperature.Initially no reaction appeared to take place before a warming of thesolution occurred. The reaction was heated under reflux at 55° C. andafter about 1 h a white rubbery solid formed as small particles. After16 h a polymeric white solid was evident, water was added and thisreacted very exothermally, attempts to filter the solution caused filterblockage. The insoluble fraction was dried at 100° C. and became quitebrittle and hard (white). This was washed in 2.0 molar hydrochloric acidand a little diethyl ether, and washed with water by filtration and withdiethyl ether by decantation (3 times). This yielded a pale brown solid.The soluble fraction was evaporated to dryness in air and formed a veryrubbery transparent solid. The solid obtained from the soluble fractionbecame mostly insoluble after drying suggesting formation of siloxane(Si—O—Si) cross-linking.

To the insoluble material (101.8 mg), bromine (11.5 μl) was added, thisreacted very slowly with the silicon network. The network was filteredand treated with diisobutylaluminum hydride (0.75 ml, 20 wt % intoluene). This was then washed with toluene followed by hexane and theinfrared and proton NMR spectra recorded.

Diisobutylaluminium hydride (0.75 ml, 20 wt % in toluene) was addeddirectly to the insoluble solid organosilicon network (72.9 mg), thesolid was then filtered and washed with toluene and diethyl ether beforethe material was dried in the atmosphere at room temperature and theinfrared and proton NMR spectra recorded.

The infrared spectra of the materials prepared all expressed absorptionpeaks in the region expected for silicon hydrogen stretching modeabsorption. Treatment of the insoluble material with bromine prior toreduction with diisobutylaluminium hydride appeared to have no effect onthe amount of silane subsequently produced. The soluble material didhowever show a more intense silicon hydride signal in the infraredspectra. The soluble material showed a more intense silicon hydridesignal in the infrared spectra. The presence of silane functions wasalso detected by proton NMR spectroscopy at 3.44 ppm, the siliconhydride triplet is observed at 3.7 ppm for tributylsilane.

Example 6

Method E, HSiCl₃ and BrMg(CH₂)₁₂MgBr

A 1.67 times excess of diGrignard reagent was prepared from1,12-dibromododecane (5.84 g, 17.8 mmol) and magnesium (0.94 g, 39.2mmol). This was added to trichlorosilane (HSiCl₃, 0.964 g, 0.719 ml,7.12 mmol) in diethyl ether. A violent reaction occurred as thediGrignard was added and a white material appeared immediately. Thewhole solution solidified into a partially white, partially transparentrubbery solid. This was then cooled to room temperature before 1 molarHCl (20 ml) was slowly added and the solid filtered and washed withwater, ethanol and finally diethyl ether. Further diethyl ether wasadded and this was heated and reflux at 55° C. for 15 h. The diethylether was removed from the soluble fraction to yield white oil thatcould be re-dispersed into organic solvents.

Example 7

Preparation of (MeHSi(CH₂)₁₂)_(n) (13) Polymers

A 1.67 times excess of diGrignard reagent was prepared fromdibromododecane (5.16 g, 15.7 mmol) and magnesium (0.85 g, 35.4 mmol) indiethyl ether (20 ml). The diGrignard was slowly added todichloromethylsilane (1.08 g, 9.39 mol) in diethyl ether (10 ml) at 0°C. This was then heated to 50° C. under reflux overnight before beingcooled to 0° C. and 1.0 molar hydrochloric acid (20 ml) slowly added.The organic phase was separated and washed with water three times anddried over magnesium sulphate. The diethyl ether was removed by rotaryevaporation to yield an oily polymer.

Materials analogous to the lead species tris-(trimethylsilyl)silane wereinvestigated, the vital aspect of the lead compound is that the hydrogencarrying silicon atom is covalently bonded to three other silicon atoms.This allows for a unique interaction of the p-orbitals allowing astabilisation of the corresponding tri-(trimethylsilyl)silyl radical bypartial delocalisation of the unpaired electron. For this reason, thesynthesis of materials in which each silicon carrying a hydrogen isconnected to three other silicon atoms was studied. The first in thisseries of networks is the very simplest material, an interconnectingnetwork of silicon wherein each silicon carries a hydrogen and is bondedto three neighbouring silicon atoms that also carry one hydrogen atom.The reduction of trichlorosilane by a metal species to give a silanenetwork of the form (HSi)_(n) was proposed.

Preparation of (HSi)_(n) (14) Network

Magnesium (0.683 g, 28.5 mmol) was dried in a shlenk flask, this wastreated with a small amount of iodine vapour before trichlorosilane(1.74 ml, 2.25 g, 16.6 mmol) was added in diethyl ether (5 ml). Thesolution was initially pale brown (iodine) but became clear and a whiteprecipitate appeared, presumably magnesium chloride.

(¹H NMR spectrum, 4.86 ppm, S1H), (FT-IR spectrum, 2250 cm⁻¹, H—SiC₃stretch, 2132 cm⁻¹, reduced trichlorosilane Si—H stretch), (Massspectrum, 265, 309, 326, 351, 368, 385, 400, 418, H₇Si₇Cl_(6-n)(OH)_(n)n=0 to 4 and H₅Si₅Cl_(5-n)(OH)_(n) n=0 to 3)

The proton NMR spectrum expressed a peak at 4.86 ppm but also showed thepresence of trichlorosilane at 7.48 ppm. The FT-IR spectrum showed twopeaks, one at 2250 cm⁻¹ corresponding to trichlorosilane, and another at2132 cm⁻¹ indicating a partial reduction of the trichlorosilane. Themass spectrum analysis revealed that the material containedH₇Si₇Cl_(6-n)(OH)_(n) n=0 to 4 and H₅Si₅Cl_(5-n) (OH)_(n) n=0 to 3.Partial reduction of the trichlorosilane occurs in this reaction, mostprobably due to the precipitation of the network as it forms. Thereduction is expected to proceed readily initially as thetrichlorosilane is a free species in the solvent, as the network beginsto grow in size, unreduced silicon may become entrapped inside the bulkmaterial. Once the network reaches a sufficient size that it begins toprecipitate the reaction is very much hindered, at this stage both themagnesium and the partially reduced trichlorosilane are in the solidphase and the reaction rate is negligible. To overcome this problem asoluble metal reducing agent was employed, sodium naphthalenide was usedto reduce the trichlorosilane.

Naphthalene (2.21 g, 17.3 mmol) was added to THF (30 ml, dry anddegassed) in a 100 ml flask, this dissolved readily to give a clearsolution. Sodium (0.79 g, 34.3 mmol) was wiped of excess oil and weighedbefore being cut into small pieces and added to the solution, afterabout 2 h the solution had become dark green. Trichlorosilane (0.44 ml,0.56 g, 4.1 mmol) in THF (20 ml) was slowly added to the sodiumnaphthalenide solution. At first the solution became white as thesolutions mixed but stirring removed this although a solid precipitatepersisted. The reaction colour changes proceeded from dark green, darkbrown, orange, yellow, to white. Sodium remained at the bottom of theflask and continued to react with the liberated naphthalene causing acolour change in the reverse order. This occurred over the course of twodays. TABLE 13 Infrared spectroscopy Absorption in Literature absorptionin cm⁻¹ cm⁻¹ Assignment 2924 and 2845 2970 to 2930 and 2980 to CH₂ andCH₃ 2845 respectively 2244 2258 Trichlorosilane Si—H stretch 2111(Me₃Si)₃Si—H type stretch 1594 1594 Naphthalene 1462 and 1377 1470 to1450 and 1380 to Methylene units 1370

The reduction of trichlorosilane by sodium naphthalenide is much morecomplete than when magnesium turnings are used. However the materialproduced in both preparations was a fine powder that did not settlereadily and so from an application viewpoint materials prepared by thismethod are of little value since filtration would be a non-trivialprocedure. The mechanism of this reduction is thought to proceed via afree radical mechanism, transfer of a single electron from thenaphthalenide ainionic radical to the trichlorosilane is postulated asthe first step. Loss of chloride from this species to give thedichlorosilane radical is expected followed by coupling of two of theseradicals and continued reduction by single electron transfers.Interestingly, the naphthalene is able to return to the sodium wherebyforming more sodium naphthalenide and thus acting catalytically.

1-45. (canceled)
 46. A polymer comprising: a structural unit (1)

wherein R is individually selected from divalent hydrocarbon radicals;R¹ is selected from the group consisting of monovalent hydrocarbonradicals, organic polymers and inorganic polymers; R² is individuallyselected from divalent hydrocarbon radicals; M is a tin, silicon orgermanium atom, preferably tin or silicon, more preferably tin; X isselected from H, Cl, Br and I; Y is selected from H, Cl, Br and I; m isan integer of 1 or 2; p is an integer of 1 or 2; q is an integer of 1 or2; r is an integer of 0 or 1; and, wherein m+p+q+r=4, or a structuralunit (2)

wherein R is individually selected from divalent hydrocarbon radicals;R¹ is selected from the group consisting of monovalent hydrocarbonradicals, H, Cl, Br, I, organic polymers and inorganic polymers; M is atin, silicon or germanium atom, preferably tin or silicon, morepreferably tin; and, m is an integer of 1-4.
 47. A polymer according toclaim 46, wherein the polymer is a hydrogenation catalyst when X is H.48. A polymer according to claim 46, comprising one or both of thefollowing structures

wherein n is an integer of 10-100000, more preferably 50-50000, morepreferably 200-10000.
 49. A polymer according to claim 46, wherein R isselected from the group consisting of C₁₋₂₀ alkanediyl, C₂₋₂₀alkenediyl, C₂₋₂₀ alkynediyl, C₃₋₃₀ cycloalkanediyl, C₃₋₃₀cycloalkenediyl, C₅₋₃₀ cycloalkynediyl, C₇₋₃₀ alkarylenediyl and C₅₋₃₀arylenediyl, any of which may be optionally substituted with one or moreheteroatoms in the carbon backbone.
 50. A polymer according to claim 46,wherein substantially all groups R are the same.
 51. A polymer accordingto claim 46, wherein R¹ is selected from the group consisting of C₁₋₂₀alkyl, C₁₋₂₀ alkoxy, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₃₋₃₀ cycloalkyl,C₃₋₃₀ cycloalkenyl, C₄₋₃₀ cycloalkynyl, C₇₋₃₀ alkaryl, C₅₋₃₀ aryl, C₅₋₃₀aryloxy, any of which may be optionally substituted with one or moreheteroatoms in the carbon backbone, organic and inorganic polymers. 52.A polymer according to claim 46, wherein R¹ is selected from the groupconsisting of methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,nonyl, dodecyl, eicosyl, norbornyl and adamantyl, vinyl, propenyl andcyclohexenyl, benzyl, phenylethyl and phenylpropyl, phenyl, tolyl,dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl,naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl,acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl,biphenylyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, phenoxy,1,2-dimethylbutoxy, preferably phenyl and phenoxy.
 53. A polymeraccording to claim 46, wherein R² is selected from the group consistingof C₁₋₂₀ alkanediyl, C₂₋₂₀ alkenediyl, C₂₋₂₀ alkynediyl, C₃₋₃₀cycloalkanediyl, C₃₋₃₀ cycloalkenediyl, C₅₋₃₀ cycloalkynediyl, C₇₋₃₀alkarylenediyl and C₅₋₃₀ arylenediyl, any of which may be optionallysubstituted with one or more heteroatoms in the carbon backbone.
 54. Apolymer according to claim 46, wherein X is individually selected fromthe group consisting of Br, I and H, most preferably Br and H.
 55. Apolymer according to claim 46, wherein Y is individually selected fromthe group consisting of Br, I and H, most preferably Br and H.
 56. Apolymer according to claim 46, wherein X′ is Cl.
 57. A polymer accordingto claim 46, wherein p in structural unit (1) is
 1. 58. A polymeraccording to claim 46, wherein q in structural unit (1) is
 1. 59. Apolymer according to claim 46 comprising structural unit (1), whereinthe polymer comprises a structural unit (7) and/or (8)

wherein R is individually selected from the group consisting of H,methyl and propyl, preferably H; X is Br or I; and, n is an integer of1-20, preferably 1-12, more preferably 6, 8, 10, or
 12. 60. A polymeraccording to claim 46 comprising structural unit (1), wherein thepolymer comprises a structural unit (9) and/or (10)

wherein R is individually selected from the group consisting of H,methyl and propyl, preferably H; R¹ is selected from the groupconsisting of C₆₋₁₀ aryl and C₆₋₁₀ aryloxy, preferably phenyl andphenyloxy; and, n is an integer of 1-20, preferably 1-12, morepreferably 6, 8, 10, or
 12. 61. A polymer according to claim 46, whereinthe molecular weight of the polymer is in the range of 100-10000000,more preferably in the range of 1000-1000000, more preferably in therange 10000-100000.
 62. A process for the production of a polymercomprising a structural unit (2)

wherein R is individually selected from divalent hydrocarbon radicals;R¹ is selected from the group consisting of monovalent hydrocarbonradicals, H, Cl, Br, I, organic polymers and inorganic polymers; M is atin, silicon or germanium atom, preferably tin or silicon, morepreferably tin; and, m is an integer of 1-4; comprising reacting adiGrignard reagent having the formula (3)XM′(R)M′X  (3) wherein X is individually selected from the groupconsisting of Cl, Br and I; M′ is individually selected from the groupconsisting of Group II metals; and, R is selected from divalenthydrocarbon radicals; with a compound having the formula (4)R¹ _(a)MX′_(b)  (4) wherein R¹ is selected from the group consisting ofmonovalent hydrocarbon radicals, H, organic polymers and inorganicpolymers; M is a tin, silicon or germanium atom, preferably tin orsilicon, more preferably tin; X is individually selected from the groupconsisting of Cl, Br and I; X′ is individually selected from the groupconsisting of Cl, Br and I; a is an integer of 0-2; and, b is an integerof 2-4.
 63. A process for the production of a polymer comprising astructural unit (1)

wherein R is individually selected from divalent hydrocarbon radicals;R¹ is selected from the group consisting of monovalent hydrocarbonradicals, organic polymers and inorganic polymers; R² is individuallyselected from divalent hydrocarbon radicals; M is a tin, silicon orgermanium atom, preferably tin or silicon, more preferably tin; X isselected from Cl, Br and I; Y is selected from Cl, Br and I; m is aninteger of 1 or 2; p is an integer of 1 or 2; q is an integer of 1 or 2;r is an integer of 0 or 1; and, wherein m+p+q+r=4; comprising reacting acompound having formula (2) as defined in claim 69 with a compoundselected from a chlorinating agent, a brominating agent and aniodinating agent.
 64. A process for the production of a polymercomprising a structural unit (1)

wherein R is individually selected from divalent hydrocarbon radicals;R¹ is selected from the group consisting of monovalent hydrocarbonradicals, organic polymers and inorganic polymers; R² is individuallyselected from divalent hydrocarbon radicals; M is a tin, silicon orgermanium atom, preferably tin or silicon, more preferably tin; X isselected from H, Cl, Br and I; Y is selected from H, Cl, Br and I; withthe proviso that at least one of X or Y is H; m is an integer of 1 or 2;p is an integer of 1 or 2; q is an integer of 1 or 2; r is an integer of0 or 1; and, wherein m+p+q+r=4; comprising reacting a polymer comprisinga structural unit (1), wherein X and Y are selected from Cl, Br and I,with a reducing agent that is a hydride source.
 65. A process accordingto claim 62, wherein M′ is selected from magnesium or calcium, mostpreferably magnesium.
 66. A process according to claim 62, wherein a is0 or
 1. 67. A process according to claim 62, wherein b is preferably 3or
 4. 68. A process according to claim 63, wherein the chlorinating,brominating and iodinating agents are Cl₂, Br₂, 12 respectively.
 69. Aprocess according to claim 64, wherein the reducing agent is selectedfrom the group consisting of borohydrides, aluminium hydrides and/orboranes; preferably lithium aluminium hydride, sodium borohydride,sodium hydride, boranes, selectride, lithium borohydride, sodiumcyanoborohydride, sodium naphthelenide, DIBAL-H and/or REDAL-H.
 70. Aprocess according to claim 64, wherein the reduction reaction isfacilitated with a radical initiator, preferably selected from the groupconsisting of 2,2′-azobisisobutyrpnitrile (AIBN), benzoyl peroxide,tert-butyl peracetate, peracetic acid, tert-amyl peroxybenzoate,tert-butylperoxide and cyclohexanone peroxide.
 71. A process for theproduction of a polymer comprising a structural unit (1)

wherein R is individually selected from divalent hydrocarbon radicals;R¹ is selected from the group consisting of monovalent hydrocarbonradicals, organic polymers and inorganic polymers; R² is individuallyselected from divalent hydrocarbon radicals; M is a tin, silicon orgermanium atom, preferably tin or silicon, more preferably tin; X isselected from H, Cl, Br and I; Y is selected from H, Cl, Br and I; withthe proviso that at least one of X or Y is H; m is an integer of 1 or 2;p is an integer of 1 or 2; q is an integer of 1 or 2; r is an integer of0 or 1; and, wherein m+p+q+r=4, comprising the steps of: (i) reacting adiGrignard reagent having the formula (3)XM′(R)M′X  (3) wherein X is individually selected from the groupconsisting of Cl, Br and I; M′ is individually selected from the groupconsisting of Group II metals; and, R is selected from divalenthydrocarbon radicals; with a compound having the formula (4)R¹ _(a)MX′_(b)  (4) wherein R¹ is selected from the group consisting ofmonovalent hydrocarbon radicals, H, organic polymers and inorganicpolymers; M is a tin, silicon or germanium atom, preferably tin orsilicon, more preferably tin; X is individually selected from the groupconsisting of Cl, Br and I; X′ is individually selected from the groupconsisting of Cl, Br and I; a is an integer of 0-2; and, b is an integerof 2-4; (ii) reacting the product of step (i) with a compound selectedfrom a chlorinating agent, a brominating agent and an iodinating agent;and, (iii) reacting the product of step (iii) with a reducing agent thatis a hydride source.
 72. A polymer comprising the structural unit (5)(HSi)_(n)  (5) wherein n is an integer.
 73. A polymer according to claim72, wherein n is an integer of 3-1000000, preferably 10-100000, morepreferably 50-50000, most preferably 200-10000.
 74. A process for theproduction of a polymer comprising a structural unit (5)(HSi)_(n)  (5) wherein n is an integer; comprising reducing a compoundhaving the formula (6)HSiX″₃  (6) wherein X″ is individually selected from the groupconsisting of Cl, Br and I.
 75. A process according to claim 74, whereinthe reducing agent is an ionic metal-containing compound.
 76. A processaccording to claim 75, wherein the reducing agent is an ionicmetal-hydrocarbon pair.
 77. A process according to claim 75, wherein thereducing agent is selected from the group consisting of ionic Group I,II, XI and XIII metal-hydrocarbon compounds.
 78. A process according toclaim 77, wherein the metal is selected from the group consisting of Li,Na, K, Mg, Ca, Cu, Hg and Zn.
 79. A process according to claim 77,wherein the hydrocarbon is selected from the group consisting ofcyclohexenyl, benzyl, phenylethyl and phenylpropyl, phenyl, tolyl,dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl,naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl,acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl andbiphenylyl anions.
 80. A process according to claim 74, wherein thereducing agent is sodium naphthalenide.